The present invention relates to triazolone compounds, use thereof and production intermediates thereof.
WO99/07687 describes that a certain kind of triazolone compounds has a fungicidal activity.
The present invention provides compounds having a fungicidal activity, particularly an excellent fungicidal activity on fungi causing plant diseases and useful for controlling plant diseases.
Namely, the present invention provides a triazolone compound of the formula [I] (hereinafter, referred to as the compound of the invention): 
wherein,
R1 represents a A1-L1-, A1-ONxe2x95x90CA2xe2x80x94, A1-ONxe2x95x90C(Me)CH2ONxe2x95x90CA2xe2x80x94, A1-C(A2)xe2x95x90Nxe2x80x94OCH2xe2x80x94, A1Sxe2x80x94C(A2)xe2x95x90Nxe2x80x94, A1-C(xe2x95x90S)NHxe2x80x94, A1Sxe2x80x94C(xe2x95x90S)NHxe2x80x94, A1Sxe2x80x94C(SA2)xe2x95x90Nxe2x80x94, A1-ONxe2x95x90C(CN)xe2x80x94, A1-ONxe2x95x90C(Me)CH2ONxe2x95x90C(CN)xe2x80x94, A1-C(CN)xe2x95x90Nxe2x80x94OCH2xe2x80x94, halogen atom, nitro or cyano;
wherein, L1 represents single bond, oxygen atom, sulfur atom, carbonyl, xe2x80x94OCH2xe2x80x94, xe2x80x94SCH2xe2x80x94, xe2x80x94C(xe2x95x90O)Oxe2x80x94, xe2x80x94OC(xe2x95x90O)xe2x80x94, xe2x80x94C(xe2x95x90O)OCH2xe2x80x94, xe2x80x94NHxe2x80x94 or C1-C6 alkylimino;
A1 and A2, which are the same or different, represent hydrogen atom, C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C3-C10 cycloalkyl, (C3-C10 cycloalkyl) C1-C10 alkyl, C5-C10 cycloalkenyl, (C5-C10 cycloalkenyl) C1-C10 alkyl, phenyl, naphthyl, phenyl C1-C10 alkyl, naphtyl C1-C10 alkyl, 5- or 6-membered heterocyclic group optionally condensed with a benzene ring, or methyl substituted by 5- or 6-membered heterocyclic group optionally condensed with a benzene ring;
the alkyl, the alkenyl, the alkynyl, the cycloalkyl, the cycloalkylalkyl, the cycloalkenyl and the cycloalkenylalkyl, represented by A1 and A2, may optionally be each substituted by one or more substituents selected from the group consisting of halogen atom(s), cyano, nitro, C1-C10 alkoxy, C1-C10 haloalkoxy, C1-C10 alkylthio, C1-C10 haloalkylthio, (C1-C9 alkyl)carbonyl, (C1-C9 alkoxy)carbonyl, (C1-C9 alkyl)carbonylamino, phenyl, phenoxy, benzyloxy and tri(C1-C10 alkyl)silyl;
the phenyl, the naphthyl, the benzene ring in the phenylalkyl, the naphthalene ring in the phenylnaphthyl, the heterocyclic group, and the heterocyclic ring in the methyl substituted by heterocylic group, represented by A1 and A2, may optionally be each substituted by one or more substituents selected from the group consisting of halogen atom(s), cyano, nitro, C1-C10 alkyl, C1-C10 haloalkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C1-C10 alkylthio, C1-C10 haloalkylthio, (C1-C9 alkyl)carbonyl, (C1-C9 alkoxy)carbonyl, (C1-C9 alkyl)carbonylamino, phenyl, phenoxy, benzyloxy, tri(C1-C10 alkyl)silyl, methylenedioxy and difluoromethylenedioxy;
with the proviso, when L1 is single bond, A1 is not a hydrogen atom;
T represents optionally substituted m-phenylene, optionally substituted m-azaphenylene (m-pyridinediyl) or optionally substituted m-diazaphenylene (m-diazinediyl, namely, m-pyridazinediyl, m-pyrimidinediyl or m-pyrazinediyl) bonded to R1 and to CH2 each via a carbon atom;
wherein the substituents are one or more substituents selected from the group consisting of halogen atoms, cyano, nitro, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio and (C1-C5 alkoxy)carbonyl;
and a fungicidal composition containing this compound as an active ingredient.
The present invention provides also 5-difluoromethyl-2-methyl-2,4-dihydro-3H-1,2,4-triazol-3-one of the formula [L]: 
a difluoroacetyl semicarbazide compound of the formula [XXVI]: 
wherein R1 and T have the same meanings as described above; a semicarbazide compound of the formula [VII]: 
wherein R1 and T have the same meanings as described above; 2-methyl-5-phenylbenzylamine of the formula [XVI-1]: 
inorganic acid salt (for example, hydrochloric acid addition salt, hydrobromic acid addition salt, sulfuric acid addition salt) and sulfonic acid salt (for example, methanesulfonic acid addition salt) of 2-methyl-5-phenylbenzylamine; 2-methyl-5-phenylbenzyl chloride of the formula [XIII-1]: 
a sulfonate compounds of the formula [XIII-2]: 
wherein R9 represents a methyl or p-tolyl; N,N-dimethyl-(2-methyl-5-phenylbenzyl)amine of the formula [LI]: 
inorganic acid salt (for example, hydrochloric acid addition salt, hydrobromic acid addition salt, sulfuric acid addition salt) and sulfonic acid salt (for example, methanesulfonic acid addition salt) of N,N-dimethyl-(2-methyl-5-phenylbenzyl)-amine, useful as a production intermediate for a compound of the invention.
In the present invention; as the C1-C10 alkyl represented by A1 and A2, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 1-methylpropyl, pentyl, 1-methylbutyl, 1-ethylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, hexyl, 1-methylpentyl, 1-ethylpentyl, 3,3-dimethylbutyl, heptyl, 3,7-dimethyloctyl and the like are listed; as the C2-C10 alkenyl represented by A1 and A2, for example, vinyl, allyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-butenyl, 2-pentenyl, 3-methyl-2-butenyl and the like are listed; as the C2-C10 alkynyl represented by A1 and A2, for example, ethynyl, proparqyl, 1-methyl-2-propynyl, 2-butynyl and the like are listed; as the C3-C10 cycloalkyl represented by A1 and A2, for example, cyclopropyl, cyclopentyl, cyclohexyl and the like are listed; as the (C3-C10 cycloalkyl)alkyl represented by A1 and A2, for example, cyclopropylmethyl, cyclopentylmethyl, 2-cyclopentylethyl, cyclohexylmethyl and the like are listed; as the C5-C10 cycloalkenyl represented by A1 and A2, for example, cyclopentenyl, cyclohexenyl and the like are listed; as the (C5-C10 cycloalkenyl)alkyl represented by A1 and A2, for example, cyclopenten-1-ylmethyl, cyclohexen-1-ylmethyl and the like are listed; as the phenyl C1-C10 alkyl represented by A1 and A2, for example, phenylmethyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl and the like are listed; as the naphthyl C1-C10 alkyl represented by A1 and A2, for example, xcex1-naphthylmethyl, xcex2-naphthylmethyl and the like are listed; as the 5- or 6-membered heterocyclic group optionally condensed with a benzene ring represented by A1 and A2, for example, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 3-pyridazinyl, 4-pyridazinyl, 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, pyrrol-1-yl, pyrrol-2-yl, pyrrol-3-yl, 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 3-isooxazolyl, 4-isooxazolyl, 5-isooxazolyl, 1-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 1-(1,2,4-triazolyl), 3-(1,2,4-triazolyl), 4-(1,2,4-triazolyl), 2-benzothienyl, 3-benzothienyl, benzothiazol-2-yl, 2-quinolyl and the like are listed; and as the methyl substituted by a 5- or 6-membered heterocyclic group optionally condensed with a benzene ring represented by A1 and A2, for example, 2-eyridylmethyl, 4-pyridylmethyl, 2-pyrimidinylmethyl, 4-pyrimidinylmethyl, 3-pyrazolylmethyl, 2-thiazolylmethyl, 2-imidazolylmethyl, 3-(1,2,4-triazolyl)methyl, 2-quinolylmethyl and the like are listed.
Here, the alkyl, the alkenyl, the alkynyl, the cycloalkyl, the cycloalkylalkyl, the cycloalkenyl and the cycloalkenylalkyl represented by A1 and A2 may optionally be each substituted by one or more substituents selected from the group consisting of halogen atom(s) (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano, nitro, C1-C10 alkoxy, C1-C10 haloalkoxy, C1-C10 alkylthio, C1-C10 haloalkylthio, (C1-C9 alkyl)carbonyl, (C1-C9 alkoxy)carbonyl, (C1-C9 alkyl)carbonylamino, phenyl, phenoxy, benzyloxy and tri(C1-C10 alkyl)silyl; and as the alkoxy, for example, a methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy, pentyloxy and the like are listed; as the haloalkoxy, for example, a trifluoromethoxy, difluoromethoxy, bromodifluoromethoxy, chlorodifluoromethoxy, fluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy and the like are listed; as the alkylthio, for example, a methylthio, ethylthio, propylthio, butylthio, isobutylthio, sec-butylthio, pentylthio, hexylthio and the like are listed, as the haloalkylthio, for example, a trifluoromethylthio, difluoromethylthio, bromodifluoromethylthio, chlorodifluoromethylthio, fluoromethylthio, 2,2,2-trifluoroethylthio, 1,1,2,2-tetrafluoroethylthio and the like are listed; as the alkylcarbonyl, for example, an acetyl, propanoyl, butanoyl, 3-methylbutanoyl andthe like are listed; as the alkoxycarbonyl, for example, a methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl and the like are listed; as the alkylcarbonylamino, for example, an acetylamino, propanylamino, butanoylamino, 3-methylbutanoylamino and the like; and as the C3-C20 trialkylsilyl, for example, a trimethylsilyl, triethylsilyl and the like are listed.
Further, the phenyl, the naphthyl, the benzene ring in the phenylalkyl, the naphthalene ring in the phenylnaphthyl, the heterocyclic group, and the heterocyclic ring in the methyl substituted by a heterocylic group, represented by A1 and A2, may optionally be each substituted by one or more substituents selected from the group consisting of halogen atom(s) (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano, nitro, C1-C10 alkyl, C1-C10 haloalkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C1-C10 alkylthio, C1-C10 haloalkylthio, (C1-C9 alkyl)carbonyl, (C1-C9 alkoxy)carbonyl, (C1-C9 alkyl)carbonylamino, phenyl, phenoxy, benzyloxy, tri (C1-C10 alkyl)silyl, methylenedioxy and difluoromethylenedioxy; and as the alkoxy, the haloalkoxy, the alkylthio, the haloalkylthio, the alkylcarbonyl, the alkoxycarbonyl, the alkylcarbonylamino and the trialkylsilyl, the same substituents as described above are listed; as the alkyl, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 1-methylpropyl, pentyl, 1-methylbutyl, 1-ethylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, hexyl, 1-methylpentyl, 1-ethylpentyl, 3,3-dimethylbutyl, heptyl, 3,7-dimethyloctyl and the like are listed; as the haloalkyl, for example, trifluoromethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl and the like are listed; and as the cycloalkyl, for example, cyclopropyl, cyclopentyl, cyclohexyl and the like are listed; and the methylenedioxy and the difluoromethylenedioxy are each substituted on adjacent two carbon atoms in a benzene ring, naphthalene ring or heterocyclic ring.
The m-phenylene, m-azaphenylene and m-diazaphenylene, bonded to R1 and to CH2 each via a carbon atom, represented by T may optionally be substituted by halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano, nitro, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylthio, C1-C6 haloalkylthio or (C1-C5 alkoxy)carbonyl; and as the alkyl, for example, methyl, ethyl and the like are listed; as the haloalkyl, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl and the like are listed; as the alkoxy, for example, methoxy, ethoxy and the like are listed; as the haloalkoxy, for example, trifluoromethoxy, difluoromethoxy, bromodifluoromethoxy, chlorodifluoromethoxy, fluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy and the like are listed; as the alkylthio, for example, methylthio, ethylthio and the like are listed; as the haloalkylthio, for example, a trifluoromethylthio, difluoromethylthio, bromodifluoromethylthio, chlorodifluoromethylthio, fluoromethylthio, 2,2,2-trifluoroethylthio, 1,1,2,2-tetrafluoroethylthioandthe like are listed; and as the alkoxycarbonyl, for example, methoxycarbonyl, ethoxycarbonyl and the like are listed.
As more specific examples of T, groups of the following formulae: 
are listed.
Among the compounds of the invention, the compounds in which R1 is optionally substituted phenyl (namely, R1 is a A1-L1-, L1 is single bond, and A1 is optionally substituted phenyl) are preferable because of an excellent fungicidal effect. Further, the compounds in which T is m-phenylene or substituted m-phenylene are preferable because of an excellent fungicidal effect, and the preferable substituents include methyl, fluorine atom, chlorine atom and trifluoromethyl.
Particularly, the compounds of the following formula [LX] in which R1 is optionally substituted phenyl and T is methylphenylene described below are preferable because of an excellent fungicidal effect. 
As the specific example of such compounds, 5-difluoromethyl-2-methyl-4-(2-methyl-5-phenylbenzyl)-2,4-dihydro-3H-1,2,4-triazol-3-one [Compound 1] of the formula: 
is mentioned.
The compound of the invention can be produced according to the following Production Method A to Production Method G. Depending on the definition of R1, a desired R1 can be introduced or structured last (for example, Production Method H). In these Production Methods, a protective group can be used for protecting a functional group from reaction, if necessary.
Production Method A
The compound of the invention of the formula [I] can be produced from a formyl compound of the formula [II] by, for example, a method shown in the following chemical reaction formula: 
wherein, R1 and T have the same meanings as described above.
The reaction temperature of the reaction of obtaining the compound of the invention of the formula [I] from the formyl compound of the formula [II] is usually in the range from xe2x88x9220xc2x0 C. to 100xc2x0 C., and the reaction time is usually in the range from 10 minutes to 10 hours. The ratio of diethylaminosulfur trifluoride used for this reaction is usually 1 to 20 mol per mol of the formyl compound of the formula [II].
The reactLion is conducted usually in a solvent, and as the solvent used, for example, halogenated hydrocarbons such as chloroform, chlorobenzene and the like, ethers such as 1,4-dioxane, tetrehydrofuran, diethyl ether and the like, aliphatic hydrocarbons such as hexane, petroleum ether and the like, aromatic hydrocarbons such as toluene, xylene and the like, and mixtures thereof are listed.
The reaction solution after completion of the reaction is subjected to post treatments such as, for example, washing with a sodium bicarbonate solution before concentration of the organic layer, and the like, giving isolation of the intended compound. This intended compound can also be purified by re-crystallization, chromatography and the like.
The formyl compound of the formula [II] can be produced, for example, according to the following scheme. 
wherein, R1 and T have the same meanings as described above, L2 represents a leaving group such as a chlorine atom, bromine atom, iodine atom, p-toluenesulfonyloxy, methanesulfonyloxy, trifluoromethanesulfonyloxy and the like, and R5 represents a C1-C5 alkyl (for example, methyl, ethyl and the like), phenyl or trihaloethyl (for example, trichloroethyl and the like).
A semicarbazide compound of the formula [VII] can be produced by reacting an isocyanate compound of the formula [III] with methylhydrazine. The reaction temperature of the reaction is usually in the range from xe2x88x9220xc2x0 C. to 50xc2x0 C., and the reaction time is usually in the range from 1 to 100 hours. The ratio of methylhydrazine used for this reaction is usually 1 to 10 mol per mol of the isocyanate compound of the formula [III]. The reaction is usually conducted in a solvent, and as the solvent used, for example, ethers such as 1,4-dioxane, tetrehydrofuran, diethyl ether and the like, halogenated hydrocarbons such as chloroform, chlorobenzene and the like, aliphatic hydrocarbons such as hexane, petroleum ether and the like, aromatic hydrocarbons such as toluene, xylene and the like, amides such as N,N-dimethylformamide and the like, dimethylsulfoxide and the like, and mixtures thereof are listed. The reaction solution after completion of the reaction is subjected to post treatments such as concentration, and the like, giving isolation of the intended compound. This intended compound can also be purified by re-crystallization, chromatography and the like. A semicarbazide compound of the formula [VIII] can be produced by reacting the isocyanate compound of the formula [III] with 1-methyl-2-hydroxyacetylhydrazine in the same manner as described above. A semicarbazide compound of the formula [IV] can also be produced by reacting the isocyanate compound of the formula [III] with hydroxyacetylhydrazine in the same manner as described above.
A compound of the formula [V] can be obtained by reacting the semicarbazide compound of the formula [IV] with a base, and for example, can be obtained by treating the compound of the formula [V] with an aqueous potassium hydroxide solution.
A compound of the formula [VI] can be obtained by reacting the semicarbazide compound of the formula [VIII] with a base, and for example, can be obtained by treating the compound of the formula [VI] with an aqueous potassium hydroxide solution.
A compound of the formula [VI] can be obtained by reacting the compound of the formula [V] with a base, and as the base used, for example, potassium carbonate is mentioned.
The compound of the formula [II] can be obtained by oxidizing the compound of the formula [VI], and as the oxidizing agent used, for example, manganese dioxide is mentioned.
The isocyanate compound of the formula [III] can be produced, for example, according to the following scheme. 
wherein, R1, L2 and T have the same meanings as described above, R6 represents a C1-C4 alkyl (for example, methyl, ethyl and the like), M1 represents silver or sodium, DIBAL represents diisobutyl aluminum hydride, BuLi represents butyllithium and DMF represents N,N-dimethylformamide.
The reaction of reacting an amine compound of the formula [XVI] with triphosgene, diphosgene or phosgene to obtain the isocyanate compound of the formula [III] can be conducted, for example, by a method described in J. Org. Chem. 61, 3883-3884 (1996) or by a method described in Intermediate Production Example 3 described later.
The reaction of reducing a nitrile compound of the formula [XV] to obtain the amine compound of the formula [XVI] can be conducted, for example, by a method of reduction using aluminum lithium hydride (LiAlH4), by a method of hydrogenating the nitrile compound of the formula [XV] in the presence of a catalyst, and by the like manner; as the catalyst used in hydrogenation, for example, Raney nickel, palladium and the like are listed. Regarding the method of using Raney nickel, JP-A No. 8-291116 can be refered, and regarding the method of using pallaridum, J. Am. Chem. Soc., 50, 3370 (1928) can be refered, respectively.
The reaction of obtaining a compound of the formula [XIII] wherein L2 represents a p-toluenesulfonyloxy, methanesulfonyloxy or trifluoromethanesulfonyloxy from an alcohol compound of the formula [XII] can be conducted, for example, according to a method described in Intermediate Production Example 12 described later.
The reaction of obtaining a compound of the formula [XIII] wherein L2 represents a chlorine atom from the alcohol compound of the formula [XII] can be conducted, for example, by a method of reacting CCl4-PPh3 to the alcohol compound of the formula [XII] (specifically, method described in Intermediate Production Example 9 described later), by a method of reacting conc. Hydrochloric acid to the alcohol compound of the formula [XII] (see, Org. Synth., IV, 576 (1967)), and by the like manner. The similar methods are applicable to the compound which L2 is bromine atom or iodine atom.
The reaction of obtaining an amine compound of the formula [XVI] from a compound of the formula [XIII] can be conducted, for example, according to a method described in J. Org. Chem., 58, 270 (1993).
Other methods in the above-mentioned scheme can be conducted by ordinary methods.
An alcohol compound of the formula [XII] wherein T is the formula: 
can also be produced from a benzyl chloride compound of the formula [XVII] according to the following chemical reaction formula: 
wherein, R10 represents a substituent inactive in Grignard reaction among substituents defined for R1.
This reaction is conducted in a solvent, and as the solvent used, ethers such as diethyl ether, tetrahydrofuran, diglyme, triglyme and the like, and mixed solvents of these ethers with aromatic hydrocarbons such as toluene, xylene and the like. If necessary, for example, J. Am. Chem. Soc., 73, 3237 (1951) can be refered.
Among the compounds of the formula [XIII], 2-methyl-5-phenylbenzyl chloride of the formula [XIII-1] can also be produced according to the following scheme. 
wherein, L2 has the same meaning as described above, and R11 represents a C1-C4 alkyl group (for example, methyl, ethyl and the like) or vinyl.
The reaction of obtaining a compound of the formula [LIII] from a compound of the formula [LII] can be conducted, for example, according to a method described in Tetrahedron, 50, 13697 (1994).
The reaction of obtaining N,N-dimethyl-(2-methyl-5-phenylbenzyl)amine of the formula [LI] from a compound of the formula [LIII] (Sommelet-Hauser rearrangement) can be conducted, for example, according to a method described in Organic Reactions, 18, 403-464 (1970). As the base used for this reaction, sodium hydride, potassium hydride, sodiumamide, potassiumamide, phenyllithium, butyllithium and the like are listed.
The reaction of obtaining 2-methyl-5-phenylbenzyl chloride of the formula [XIII-1] from N,N-dimethyl-(2-methyl-5-phenyl)benzylamine can be conducted, for example, according to a method described in Tetrahedron Lett., 24, 3233 (1983).
Production Method B
The compound of the invention of the formula [I] can be produced from a triazolone compound of the formula [XIX] according to the following chemical reaction formula. 
wherein, R1, L2 and T have the same meanings as described above.
The reaction is conducted usually in the presence of a base, and as the base used, for example, inorganic bases such as sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and the like are listed.
The reaction temperature of the reaction of obtaining the compound of the invention of the formulae [I] from a triazolone compound of the formula [XIX] is usually in the range from xe2x88x9220xc2x0 C. to 100xc2x0 C., and the reaction time is usually in the range from 1 to 100 hours.
Regarding the amounts of reagents used for the reaction, the ratio of a methylating agent of the formula [IX] is 1 to 5 mol and the ratio of the base is 1 to 10 mol, per mol of the triazolone compound of the formula [XIX].
The reaction is conducted in a solvent if necessary, and as the solvent used, for example, ethers such as 1,4-dioxane, tetrehydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, t-butyl methyl ether and the like, aliphatic hydrocarbons such as hexane, heptane, ligroin, petroleum ether and the like, aromatic hydrocarbons such as toluene, xylene and the like, organic bases such as pyridine, triethylamine, N-methylaniline, N,N-dimethylaniline, N,N-diethylaniline and the like, nitriles such as acetonitrile, isobutylonitrile and the like, N,N-dimethylformamide, dimethyl sulfoxide, water and the like, and mixtures thereof are listed. These solvents are selected depending on the kind of a base used.
The reaction solution after completion of the reaction is subjected to usual post treatments such as extraction with an organic solvent, concentration and the like, giving isolation of the intended compound. This intended compound can also be purified by re-crystallization, chromatography and the like.
The triazolone compound of the formula [XIX] can be produced, for example, according to the following scheme. 
wherein, R1, L2 and T have the same meanings as described above, and M2 represents sodium or potassium.
An isothiocyanate compound of the formula [XXI] can be produced by reacting a compound of the formula [XIII] with a compound of the formula [XX]. A thiosemicarbazide compound of the formula [XXII] can be produced by reacting the isothiocyanate compound of the formula [XXI] with hydrazine (anhydrous hydrazine or water-containing hydrazine). A triazolinethion compound of the formula [XXIII] can be produced by reacting the thiosemicarbazide compound of the formula [XXII] with difluoroacetic acid. A sulfonic acid compound of the formula [XXIV] can be produced by oxidizing the triazolinethion compound of the formula [XXIII] using an oxidizing agent (for example, hydrogen peroxide). The triazolone compound of the formula [XIX] can be produced by hydrolyzing the sulfonic acid compound of the formula [XXIV] using an acid (for example, hydrochloric acid). In conducting processes starting from a thiosemicarbazide compound of the formula [XXII] to a triazolone compound of the formula [XIX], for example, JP-A No. 7-196630 can be referred.
The reaction solution after completion of the reaction is subjected to usual post treatments such as extraction with an organic solvent, concentration and the like, giving isolation of the intended compound. This intended compound can also be purified by re-crystallization, chromatography and the like.
Production Method C
The compound of the invention of the formula [I] can be produced from a semicarbazide compound of the formula [VII], for example, according to the following chemical reaction formula. 
wherein, R1 and T have the same meanings as described above.
The reaction temperature of the above-mentioned reaction of obtaining the compound of the invention of the formula [I] from a semicarbazide compound of the formula [VII] is usually in the range from xe2x88x9220xc2x0 C. to 100xc2x0 C., and the reaction time is usually in the range from 1 to 100 hours.
Regarding the amounts of reagents used for the reaction, the ratio of a difluoroacetic anhydride is usually 1 to 5 mol per mol of the semicarbazide compound of the formula [VII].
The reaction is usually conducted in a solvent, and as the solvent used, for example, aromatic hydrocarbons such as toluene, xylene and the like, ethers such as 1,4-dioxane, tetrehydrofuran, diethyl ether and the like, aliphatic hydrocarbons such as hexane, petroleum ether and the like, and mixtures thereof are listed.
In this reaction, a difluoroacetyl semicarbazide compound of the formula [XXVI] described later is formed as a by-product in some cases, however, it can be separated off by purifying the intended compound by chromatography and the like. The separated difluoroacetyl semicarbazide compound of the formula [XXVI] can be utilized as a starting material for Production Method F described later.
The reaction solution after completion of the reaction can be, for example after decomposition of excess difluoroacetic anhydride by a base such as an aqueous sodium hydroxide solution and the like, subjected to post treatment operations such as extraction with an organic solvent, concentration and the like, giving isolation of the intended compound. This intended compound can also be purified by re-crystallization, chromatography and the like.
Production Method D
The compound of the invention of the formula [I] can be produced from the semicarbazide compound of the formula [VII], for example, according to the following chemical reaction formula. 
wherein, R1 and T have the same meanings as described above, and R7 represents a C1-C4 alkyl (for example, methyl, ethyl and the like).
The reaction temperature of the above-mentioned reaction of obtaining the compound of the invention of the formula [I] from the semicarbazide compound of the formula [VII] is usually in the range from xe2x88x9220xc2x0 C. to 100xc2x0 C., and the reaction time is usually in the range from 1 to 100 hours.
Regarding the amounts of reagents used for the reaction, the ratio of a compound of the formula [XXV] is usually 1 to 100 mol per mol of the semicarbazide compound of the formula [VII].
The reaction is conducted in the presence of a base, and as the base used, for example, metal alkoxides such as sodium methoxide, sodium ethoxide, potassium t-butoxide and the like, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and the like, alkaline earth metal hydroxides such as calcium hydroxide, magnesium hydroxide and the like, and organic bases such as triethylamine, pyridine and the like are listed, and the ratio of a base is usually 0.1 to 3 mol per mol of the semicarbazide compound of the formula [VII]
The reaction is conducted in a solvent if necessary, and as the solvent used, for example, alcohols such as methanol, ethanol and the like, ethers such as 1,4-dioxane, tetrehydrofuran, diethyl ether and the like, aliphatic hydrocarbons such as hexane, petroleum ether and the like, aromatic hydrocarbons such as toluene, xylene and the like, amides such as N,N-dimethylformamide and the like, dimethylsulfoxide and the like, and mixtures thereof are listed.
In this reaction, a difluoroacetyl semicarbazide compound of the formula [XXVI] described later is formed as a by-product in some cases, however, it can be separated off by purifying the intended compound by chromatography and the like. The separated difluoroacetyl semicarbazide compound of the formula [XXVI] can be utilized as a starting material for Production Method F described later.
The reaction solution after completion of the reaction can be, after neutralization or concentration if necessary, subjected to post treatment operations such as extraction with an organic solvent, concentration and the like, giving isolation of the intended compound. This intended compound can also be purified by re-crystallization, chromatography and the like.
Production Method E
The compound of the invention of the formula [I] can be produced from a semicarbazide compound of the formula [VII], for example, according to the following chemical reaction formula. 
wherein, R1 and T have the same meanings as described above.
The reaction temperature of the above-mentioned reaction of obtaining the compound of the invention of the formula [I] from the semicarbazide compound of the formula [VII] is usually in the range from 20xc2x0 C. to 100xc2x0 C., and the reaction time is usually in the range from 1 to 100 hours.
Regarding the amounts of reagents used for the reaction, the ratio of difluoroacetic acid is usually 1 to 100 mol per mol of the semicarbazide compound of the formula [VII].
The reaction is conducted in a solvent if necessary, and as the solvent used, for example, aromatic hydrocarbons such as toluene, xylene and the like, aliphatic hydrocarbons such as hexane, petroleum ether and the like, ethers such as 1,4-dioxane, tetrahydrofuran and the like, and mixtures thereof are listed.
In this reaction, the difluoroacetyl semicarbazide compound of the formula [XXVI] described later is formed as a by-product in some cases, however, it can be separated off by purifying the intended compound by chromatography and the like. The separated difluoroacetyl semicarbazide compound of the formula [XXVI] can be utilized as a starting material for Production Method F described later.
The reaction solution after completion of the reaction can be, after neutralization or concentration if necessary, subjected to post treatment operations such as extraction with an organic solvent, concentration and the like, giving isolation of the intended compound. This intended compound can also be purified by re-crystallization, chromatography and the like.
Production Method F
The compound of the invention of the formula [I] can be produced from the difluoroacetyl semicarbazide compound of the formula [XXVI], for example, according to the following chemical reaction formula. 
wherein, R1 and T have the same meanings as described above.
The reaction temperature of the reaction of obtaining the compound of the invention of the formula [I] from the difluoroacetyl semicarbazide compound of the formula [XXVI] is usually in the range from 20xc2x0 C. to 100xc2x0 C., and the reaction time is usually in the range from 10 minutes to 10 hours.
The reaction is conducted in the presence of a base or acid, and as the base used, for example, metal alkoxides such as sodium methoxide, sodium ethoxide, potassium t-butoxide and the like, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and the like, alkaline earth metal hydroxides such as calcium hydroxide, magnesium hydroxide and the like, and organic bases such as triethylamine, pyridine and the like are listed. The ratio of the base used is usually 0.1 to 10 mol per mol of a difluoroacetyl semicarbazide compound of the formula [XXVI]. As the acid used, for example, organic acids such as difluoroacetic acid, trifluoroacetic acid and the like are listed, and the ratio of the acid used is usually 1 to 100 mol per mol of the difluoroacetyl semicarbazide compound of the formula [XXVI].
The reaction is conducted in a solvent if necessary, and as the solvent used, for example, alcohols such as methanol, ethanol and the like, ethers such as 1,4-dioxane, tetrahydrofuran, diethyl ether and the like, aliphatic hydrocarbons such as hexane, petroleum ether and the like, aromatic hydrocarbons such as toluene, xylene and the like, amides such as N,N-dimethylformamide and the like, sulfoxides such as dimethyl sulfoxide and the like, water and mixtures thereof are listed. These solvents are selected and used depending on the kinds of an acid and base used.
The reaction solution after completion of the reaction can be, after neutralization or concentration if necessary, subjected to post treatment operations such as extraction with an organic solvent, concentration and the like, giving isolation of the intended compound. This intended compound can also be purified by re-crystallization, chromatography and the like.
The difluoroacetyl semicarbazide compound of the formula [XXVI] can also be obtained as a by-product in Production Methods C, D and E, however, can be produced, for example, according to the following scheme. 
wherein, R1 and T have the same meanings as described above.
The reaction temperature in obtaining the difluoroacetyl semicarbazide compound of the formula [XXVI] from the isocyanate compound of the formula [III] is usually in the range from 0xc2x0 C. to 100xc2x0 C., and the reaction time is usually in the range from 1 to 10 hours.
The ratio of Nxe2x80x2-methyl-difluoroacetohydrazide used for the reaction is usually 1 to 10 mol per mol of the isocyanate compound of the formula [III].
The reaction is conducted in a solvent if necessary, and as the solvent used, for example, alcohols such as methanol, ethanol and the like, ethers such as 1,4-dioxane, tetrahydrofuran, diethyl ether and the like, halogenated hydrocarbons such as chloroform, chlorobenzene and the like, aliphatic hydrocarbons such as hexane, petroleum ether and the like, aromatic hydrocarbons such as toluene, xylene and the like, amides such as N,N-dimethylformamide and the like, dimethylsulfoxide and the like, and mixtures thereof are listed.
The reaction solution after completion of the reaction is subjected, after concentration, to post treatment operations such as extraction with an organic solvent, concentration and the like, giving isolation of the intended compound. This intended compound can also be purified by re-crystallization, chromatography and the like.
Production Method G
The compound of the invention of the formula [I] can be produced from a compound of the formula [XIII] and a triazolone compound of the formula [L], for example, according to the following chemical reaction formula. 
wherein, R1, L2 and T have the same meanings as described above.
The reaction is conducted in the presence of a base, and as the base used, inorganic bases such as lithium hydroxide, lithium hydride, sodium hydroxide, sodium hydride, potassium hydroxide, potassium hydride, sodium carbonate, potassium carbonate, and the like are listed. The reaction temperature is usually in the range from 0xc2x0 C. to 100xc2x0 C., and the reaction time is usually in the range from 1 to 100 hours.
Regarding the amounts of reagents used for the reaction, the ratio of the triazolone compound of the formula [L] is usually 1 to 5 mol and the ratio of a base is usually from 1 to 10 mol per mol of the compound of the formula [XIII].
The reaction is conducted in a solvent if necessary, and as the solvent used, for example, alcohols such as methanol, ethanol and the like, ethers such as 1,4-dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and the like, aromatic hydrocarbons such as toluene, xylene and the like, organic bases such as pyridine, triethylamine, N-methylaniline, N,N-dimethylaniline, N,N-diethylaniline and the like, nitriles such as acetonitrile, isobutylonitrile and the like, N,N-dimethylformamide, dimethyl sulfoxide, water and the like, and mixtures thereof are listed. These solvents are selected depending on the kinds of a base used.
The reaction solution after completion of the reaction is subjected to post treatment operations such as extraction with an organic solvent, concentration and the like, giving isolation of the intended compound. This intended compound can also be purified by re-crystallization, chromatography and the like.
The triazoline compound of the formula [L] can be produced, for example, according to the following chemical reaction formula. 
The reaction temperature in obtaining the triazolone compound of the formula [L] from 2-methyl semicarbazide is usually in the range from 50xc2x0 C. to 150xc2x0 C., and the reaction time is usually in the range from 1 to 100 hours.
The ratio of difluoroacetic acid used for the reaction is usually 1 to 100 mol per mol of 2-methyl semicarbazide.
The reaction is conducted in a solvent if necessary, and as the solvent used, for example, aromatic hydrocarbons such as toluene, xylene and the like, aliphatic hydrocarbons such as hexane, petroleum ether and the like, ethers such as 1,4-dioxane, tetrahydrofuranand the like, and mixtures thereof are listed.
In this reaction, 1-difluoroacetyl-2-methyl semicarbazide is formed as a by-product in some cases, however, it can be separated off by purification by chromatography and the like.
The reaction solution after completion of the reaction can be, after neutralization or concentration if necessary, subjected to post treatment operations such as extraction with an organic solvent, concentration and the like, giving isolation of the intended compound. This intended compound can also be purified by re-crystallization, chromatography and the like.
The triazolone compound of the formula [L] can be shown as tautomers described below. 
2-methyl semicarbazide can be produced, for example, according to the following chemical reaction formula. 
wherein, M3 represents sodium or potassium.
This reaction is conducted usually in an acidic aqueous solution (for example, hydrochloric acid).
Trimethylsilyl isocyanate of the above-mentioned formula in which M3 represents a trimethylsilyl is reacted with methylhydrazine, then, the reaction product is reacted with methanol. Thus, 2-methyl semicarbazide can be produced.
Production Method H
Production can be effected by the following methods (H-1) to (H-6).
(H-1): Method of producing the compound of the invention of the formula [I-2] wherein R1 in the formula [I] is phenyl, naphthyl or heterocyclic group 
wherein, R8 represents phenyl, naphthyl or heterocyclic group, and the phenyl, naphthyl or heterocyclic group may optionally be each substituted by one or more substituents selected from the group consisting of halogen atoms, cyano, nitro, C1-C10 alkyl, C1-C10 haloalkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C1-C10 alkylthio, C1-C10 haloalkylthio, (C1-C9 alkyl) carbonyl, (C1-C9 alkoxy)carbonyl, (C1-C9 alkyl)carbonylamino, phenyl, phenoxy, benzyloxy, C3-C20 Lrialkylsilyl, methylenedioxy and difluoromethylenedioxy; X and Z are the same or different and represent a chlorine atom, bromine atom, iodine atom or trifluoromethanesulfonyloxy; and T has the same meaning as described above.
(1) Method of producing aborate compound of the formula [XXVIII]
A borate compound of the formula [XXVIII] can be produced by reacting a compound of the formula [I-1] with bis(pinacolate)diboron in an organic solvent (for example, dimethyl sulfoxide, dimethylformamide) in the presence of a base (for example, potassium acetate, potassium carbonate) and a palladium catalyst (for example, dichloromethane complex of [bis(diphenylphosphino)ferrocene]dichloropalladium (II), tetrakistriphenylphosphinepalladium).
The reaction solution after completion of the reaction can be added to water, then, subjected to post treatments such as extraction with an organic solvent, concentration and the like, giving isolation of the intended compound. This intended compound can also be purified by chromatography and the like.
In this reaction, J. Org. Chem., 60, 7508-7510 (1995) can be refered, if necessary.
(2) Method of producing a compound of the invention of the formula [I-2]
The compound of the invention of the formula [I-2] can be produced by reacting the borate compound of the formula [XXVIII] with a compound of the general formula R8Z in an organic solvent (for example, dimethoxyethane) in the presence of a base (for example, potassium phosphate, potassium carbonate) and a palladium catalyst (for example, dichloromethane complex of [bis(diphenylphosphino)ferrocene]dichloropalladium (II), palladiumacetate (II), tetrakistriphenylphosphinepalladium, mixtures thereof).
A solvent in the reaction solution after completion of the reaction is distilled off, for example, then, the residue is subjected to chromatography, or the reaction solution after completion of the reaction is subjected to post treatments such as extraction with an organic solvent, concentration and the like. Thus the intended compound can be obtained. This intended compound can also be purified by re-crystallization, chromatography and the like.
In this reaction, TetrahedronLett., 38, 7645-7648 (1997) can be refered, if necessary. (H-2) Method shown in the following chemical reaction formula {method of producing the compound of the invention of the formula [I-3] wherein R1 in the formula [I] is an alkynyl having a triple bond at the bonding end}
wherein, A3xe2x80x94Cxe2x89xa1C represents a C2-C10 alkynyl optionally substituted having a triple bond at the end. This alkynyl may optionally be substituted by one or more substituents selected from the group consisting of halogen atoms, cyano, nitro, C1-C10 alkoxy, C1-C10 haloalkoxy, C1-C10 alkylthio, C1-C10 haloalkylthio, (C1-C9 alkyl)carbonyl, (C1-C9 alkoxy)carbonyl, (C1-C9 alkyl) carbonylamino, phenyl, phenoxy, benzyloxy and C3-C20 trialkylsilyl; and T and X are the same as described above.
The reaction of obtaining a compound of the invention of the formula [I-3] from a compound of the formula [I-1] can be conducted, for example, in an aprotic polar solvent (for example, acetonitrile, N,N-dimethylformamide) in the presence of a base (for example, secondary amine such as disopropylamine and the like, tertiary amine such as triethylamine and the like) anda catalyst (for example, combination of triphenylphosphine, copper iodide (I) and palladium catalyst such as bis(triphenylphosphine)dichloropalladium {PdCl2(PPh3)2} and the like). If necessary, WO98/03464, Example 1, Tetrahedron Lett., 16, 4467-4470 (1975), Synthesis, 1980, 627-630, or J. Org. Chem., 64, 2070-2079 (1999) can be referred.
The reaction solution after completion of the reaction can be subjected to post treatment operations such as extraction with an organic solvent, concentration and the like, to obtain the intended compound. This intended compound can also be purified by re-crystallization, chromatography and the like. (H-3) Method shown in the following chemical reaction formula {method of producing a compound of the invention of the formula [I-2] wherein R1 in the formula [I] represents a phenyl, naphthyl or heterocyclic group}
wherein, R8, T and X are the same as described above.
The reaction of obtaining the compound of the invention of the formula [I-2] from a compound of the formula [I-1] can be conducted, for example, in a mixed solvent of water and diethoxyethane in the presence of a base (for example, inorganic base such as sodium bicarbonate) and a catalyst (for example, tetrakis(triphenyl)phosphinepalladium {Pd(PPh3)4}) (If necessary, see description in WO96/35669, Beispiel 2), or in a solvent in the presence of tetrabutylammonium bromide, base (for example, inorganic base such as potassium carbonate) and catalyst (for example, palladium acetate). The reaction solution after completion of the reaction can be subjected to post treatment operations such as extraction with an organic solvent, concentration and the like, to obtain the intended compound. This intended compound can also be purified by re-crystallization, chromatography and the like. If necessary, J. Org. Chem., 62, 7170-7173(1997) can be referred, for example. (H-4) Method shown in the following scheme {method of producing a compound of the invention of the formula [I-5] wherein R1 in the formula [I] represents a phenoxy, naphthyloxy or heterocyclic-oxy optionally substituted}
wherein, X and T have the same meanings as described above, and A4 represents a phenyl, naphthyl or heterocyclic group, and the phenyl, naphthyl or heterocyclic group may optionally each be substituted by one or more substituents selected from the group consisting of halogen atoms, cyano, nitro, C1-C10 alkyl, C1-C10 haloalkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C1-C10 alkylthio, C1-C10 haloalkylthio, (C1-C9 alkyl) carbonyl, (C1-C9 alkoxy)carbonyl, (C1-C9 alkyl)carbonylamino, phenyl, phenoxy, benzyloxy, C3-C20 trialkylsilyl, methylenedioxy and difluoromethylenedioxy.
(1) Method of production from a compound of the formula [I-4]
The reaction of obtaining a compound of the invention of the formula [I-5] from a compound of the formula [I-4] can be conducted in an organic solvent (for example, methylene chloride) in the presence of a base (for example, organic base such as triethylamine and the like, inorganicbase such as sodium bicarbonate and the like) and a catalyst (for example, copper acetate (II)). If necessary, Tetrahedron Lett., 39, 2937-2940 (1998) can be refered.
(2) Method of production from a compound of the formula [I-1]
The reaction of obtaining a compound of the invention of the formula [I-5] from a compound of the formula [I-1] can be conducted in an organic solvent (for example, toluene, ethyl acetate) in the presence of a base (for example, organic base such as triethylamine and the like, inorganic base such as potassium carbonate, cesium carbonate and the like) and a catalyst (for example, copper iodide (I)). The reaction solution after completion of the reaction can be subjected to post treatment operations such as extraction with an organic solvent, concentration and the like, to obtain the intended compound. This intended compound can also be purified by re-crystallization, chromatography and the like.
In this reaction, if necessary, descriptions in J. Amer. Chem. Soc., 119, 10539-10540 (1997), J. Amer. Chem. Soc., 121, 3224-3225 (1999) and J. Amer. Chem. Soc., 121, 4369-4378 (1999) can be refered.
(3) Method of production from a compound of the formula [XXVIII]
The reaction of obtaining a compound of the invention of the formula [I-5] from a compound of the formula [XXVIII] can be conducted in an organic solvent (for example, methylene chloride) in the presence of a base (for example, organic base such as triethylamineand the like, inorganicbase such as sodium bicarbonate and the like) and a catalyst (for example, copper acetate (II)). If necessary, descriptions in Tetrahedron Lett., 39, 2937-2940 (1998) can be referred.
(H-5) Method shown in the following scheme {method of producing compounds of the inventionof the formulae [I-7] and [I-8] wherein R1 in the formula [I] represents a A1-ONxe2x95x90CA2xe2x80x94}
wherein, A5 represents a group other than a hydrogen atom among represented by A1, and L2, A2 and T have the same meanings as described above.
Compounds of the formula [I-7] in which A2 is a methyl can be produced from a compound of the formula [I-6] according to a method described in J. Org. Chem., 57, 1481-1486 (1992). Other compounds can also be produced by ordinary methods according to the above-mentioned scheme. (H-6) Method shown in the following scheme 
wherein, A1, A2, L2 and T have the same meanings as described above.
Each process in the above-mentioned scheme can be conducted according to an ordinary method.
When the compound of the invention is used as an active ingredient of a fungicidal composition, it may be used itself without adding any other components, however, it is usually mixed with solid carriers, liquid carriers, surfactants and other adjuvants, to prepare emulsifiable concentrates, wettable powders, water dispersible granules, emulsion formulation, flowables, dust formulation, granules and the like, tobe used. These formulations contain the compound of the invention as an active ingredient in an amount of usually from 0.1 to 90 wt %.
The solid carrier to be used in the formulation may include, for example, the following materials in fine powder or granule form: mineral materials (e.g., kaolinite clay, attapulgite clay, bentonite clay, montmorillonite clay, acid clay, pyrophyllite, talc, diatomaceous earth, calcite), natural organic materials (e.g., stalks of corn, powder of wallnut-shell), synthetic organic materials (e.g., urea), salts (e.g., calciumcarbonate, ammonium sulfate) and synthetic inorganic materials (e.g., synthetic hydrated silicon oxide). The liquid carrier may include, for example, aromatic hydrocarbons (e.g., xylene, alkylbenzene, methylnaphthalene), alcohols (e.g., isopropyl alcohol, ethylene glycol, propylene glycol, ethylene glycol mono-ethyl ether), ketones (e.g., acetone, cyclohexanone, isophorone), vegetable oils (e.g., soybean oil, cotton seed oil), petroleum aliphatic hydrocarbons, esters, dimethyl sulufoxide, acetonitrileandwater. The surfactant may include, for example, anionic surfactants (e.g., alkylsulfate ester salts, alkyl (aryl) sulfonic acid salts, dialkylsulfosuccinic acid salts, phosphate salts of polyoxyethylenealkyl aryl ether, lignin sulfonic acid salts, naphthalenesulfonic acid formaldehyde condensations), nonionic surfactants (e.g., polyoxyethylene alkyl aryl ethers, polyoxyethylene propylene block copolymer, sorbitan fatty acid esters). The other adjuvants may include, for example, water-soluble polymers (e.g., polyvinyl alcohol, polyvinylpyrrolidone), polysaccharides (e.g., gumarabic, alginic acidand their salts, CMC (carboxy methyl cellulose), xanthan gum), inorganic materials (aluminum magnesium silicate, alumina sol), preservatives, coloringagents, PAP (isopropylacidphosphate), BHT.
The method of the application of the compound of the invention is concretely carried out, for example, by a foliar treatment, by a soil treatment, by a seed treatment and the like, also it is carried out by any method which is usually a person in the art uses.
When the compound of the invention is applied as the active ingredient of the fungicidal composition, the application amount of the active ingredient; although it may vary with a variety of plants (crops) to be protected, a variety of plant diseases to be controlled, a extent of disease damage, a formulation type, an application type, application times, weather condition and the like; is usually 1 to 5,000 g per hectare, preferably 5 to 1,000 g per hectare. In the case of emulsifiable concentrates, wettable powders, flowables and the like, they are usually applied after diluted with water, usually at a concentration of 0.0001 to 3% by weight, preferably at a concentration of 0.0005 to 1% by weight as active ingredients of the invention. In the case of dust formulations, granules and the like, they are usually applied as it is without diluting.
The compound of the invention can be used as a agricultural and horticultural antifungal agent in agricultural fields, paddy fields, orchards, tea plantations, grasslands, lawnsand the like. Increasing of the antifungal effect may be expected by using the compound of the invention with other agricultural and horticultural antifungal agent(s).
Example of the other agricultural and horticultural antifungal agents include:
azole antifungal compound such as propiconazole, triadimenol, prochloraz, penconazole, tebuconazole, flusilazole, diniconazole, bromoconazole, epoxyconazole, difenoconazole, cyproconazole, metconazole, triflumizole, tetraconazole, myclobutanil, fenbuconazole, hexaconazole, fluquinconazole, triticonazole, bitertanol, ipconazole, imibenconazole, imazalil, flutriafol and the like; cyclic amine antifungal compound such as fenpropimorph, tridemorph, fenpropidin and the like; benzimidazole antifungal compound such as carbendazim, benomyl, thiabendazole, thiophanate-methyl and the like; ethylen bis(dithiocarbamate) compound such as maneb, zineb, mancozeb and the like; phthalimide compound such as captan, folpet and the like; inorganic copper such as basic copper chloride, basic copper sulfate, copper sulfate, copper hydroxide and the like; organic copper such as copper-oxinate, copper-nonylphenol-sulfonate and the like; procymidone, cyprodinil, pyrimethanil, diethofencarb, thiuram, fluazinam, iprodione, vinclozolin, chlorothalonil, mepanipyrim, fenpiclonil, fludioxonil, dichlofluanid, folpet, kresoxim-methyl, azoxystrobin, trifloxystrobin, picoxystrobin, N-methyl-xcex1-methoxyimino-2-[(2,5-dimethylphenoxy)methyl]phenylacetamide, spiroxamine, quinoxyfen, fenhexamid, famoxadone, fenamidone (RP-407213), iprovalicarb, iminoctadine-triacetate, iminoctadine-albesilate, 6-iodo-3-propyl-2-propoxy-4 (3H)-quinazolinone, (Z)-N-(xcex1-cyclopropylmethoxyimino-2,3-difluoro-6-(trifluoro methyl)benzyl)-2-phenylacetamide, 2-chloro-N-(4xe2x80x2-chloro-(1,1xe2x80x2-biphenyl)-2-yl)-3-piridinecarboxamide, N-[2-(1,3-dimethylbutyl)-3-thienyl]-2,4-dimethylthiazole-5-carboxamide, N-[2-(1,3-dimethylbutyl)-3-thienyl]-3-trifluoromethyl-1-methylpyrazole-4-carboxamide and the like.
In the case of using the mixture of the compound of the invention and azole antifungal compound, the ratio of the compound of the invention to azole antifungal compound as the active ingredients is not limited to specific ratio; but when the ratio of azole antifungal compound to the compound of the invention by weight is 0.25 to 4, the excellent synergic effect can be achieved. In the case of using the mixture of the compound of the invention and cyclic amine antifungal compound, the ratio of the compound of the invention to cyclic amine antifungal compound as the active ingredients is not limited to specific ratio; but when the ratio of cyclic amine antifungal compound to the compound of the invention by weight is 1 to 8, the excellent synergic effect can be achieved. In the case of using the mixture of the compound of the invention and quinoxyfen, the ratio of the compound of the invention to quinoxyfen as the active ingredients is not limited to specific ratio; but when the ratio of quinoxyfen to the compound of the invention by weight is 0.25 to 2, the excellent synergic effect can be achieved. In the case of using the mixture of the compound of the invention and spiroxamine, the ratio of the compound of the invention to spiroxamine as the active ingredients is not limited to specific ratio; but when the ratio of spiroxamine to the compound of the invention by weight is 1 to 8, the excellent synergic effect can be achieved. In the case of using the mixture of the compound of the invention and ethylen bis (dithiocarbamate) compound, the ratio of the compound of the invention to ethylen bis(dithiocarbamate) compound as the active ingredients is not limited to specific ratio; but when the ratio of ethylen bis(dithiocarbamate) compound to the compound of the invention by weight is 1 to 20, the excellent synergic effect can be achieved. In the case of using the mixture of the compound of the invention and phthalimide compound, the ratio of the compound of the invention to phthalimide compound as the active ingredients is not limited to specific ratio; but when the ratio of phthalimide compound to the compound of the invention by weight is 1 to 20, the excellent synergic effect can be achieved. In the case of using the mixture of the compound of the invention and inorganic copper or organic copper, the ratio of the compound of the invention to inorganic copper or organic copper as the active ingredients is not limited to specific ratio; but when the ratio of inorganic copper or organic copper to the compound of the invention by weight is 1 to 20, the excellent synergic effect can be achieved. In the case of using the mixture of the compound of the invention and 6-iodo-3-propyl-2-propoxy-4(3H)-quinazolinone or (Z)-N-(xcex1-cyclopropylmethoxyimino-2,3-difluoro-6-(trifluoromethyl)benzyl)-2-phenylacetamide, the ratio of the compound of the invention to 6-iodo-3-propyl-2-propoxy-4(3H)-quinazolinone or (Z)-N-(xcex1-cyclopropylmethoxyimino-2,3-difluoro-6-(trifluoromethyl)benzyl)-2-phenylacetamide as the active ingredients is not limited to specific ratio; when the ratio of 6-iodo-3-propyl-2-propoxy-4(3H)-quinazolinone or (Z)-N-((-cyclopropylmethoxyimino-2,3-difluoro-6-(trifluoromethyl)benzyl)-2-phenylacetamide to the compound of the invention by weight is 0.1 to 4, the excellent synergic effect can be achieved. In the case of using the mixture of the compound of the invention and 2-chloro-N-(4xe2x80x2-chloro-(1,1xe2x80x2-biphenyl)-2-yl)-3-piridinecarboxamide, N-[2-(1,3-dimethylbutyl)-3-thienyl]-2,4-dimethylthiazole-5-carboxamide or N-[2-(1,3-dimethylbutyl)-3-thienyl]-3-trifluoromethyl-1-methylpyrazole-4-carboxamide, the ratio of the compound of the invention to 2-chloro-N-(4xe2x80x2-chloro-(1,1xe2x80x2-biphenyl)-2-yl)-3-piridinecarboxamide, N-[2-(1,3-dimethylbutyl)-3-thienyl]-2,4-dimethylthiazole-5-carboxamide or N-[2-(1,3-dimethylbutyl)-3-thienyl]-3-trifluoromethyl-1-methylpyrazole-4-carboxamide as the active ingredients is not limited to specific ratio; but when the ratio of 2-chloro-N-(4xe2x80x2-chloro-(1,1xe2x80x2-biphenyl)-2-yl)-3-piridinecarboxamide, N-[2-(1,3-dimethylbutyl)-3-thienyl]-2,4-dimethylthiazole-5-carboxamideorN-[2-(1,3-dimethylbutyl)-3-thienyl]-3-trifluoromethyl-1-methylpyrazole-4-carboxamide to the compound of the invention by weight is 0.2 to 5, the excellent synergic effect can be achieved.
6-Iodo-3-propyl-2-propoxy-4(3H)-quinazolinone is a compound described in WO94/26722, (Z)-N-(xcex1-cyclopropylmethoxyimino-2,3-difluoro-6-(trifluoromethyl)benzyl)-2-phenylacetamide is a compound described in WO96/19442, 2-chloro-N-(4xe2x80x2-chloro-(1,1xe2x80x2-biphenyl)-2-yl)-3-piridinecarboxamide is a compound described in EP545099A, N-[2-(1,3-dimethylbutyl)-3-thienyl]-2,4-dimethylthiazole-5-carboxamide and N-[2-(1,3-dimethylbutyl)-3-thienyl]-3-trifluoromethyl-1-me thylpyrazole-4-carboxamide are compounds JP-H09-235282-A.
The compound of the invention can be applied after mixed with other agricultural and horticultural insecticidal agent(s), acaricidal agent(s), nematocidal agent(s), herbicidal agent(s), plant growth controlling agent(s) or fertilizer(s). And also the compound of the invention can be applied at the same time without mixing it beforehand.
Examples of the insecticides and acaricides include: organophosphorus compounds such as fenitrothion [O,O-dimethyl O-(3-methyl-4-nitrophenyl)phosphorothioate], fenthion [O,O-dimethyl O-(3-methyl-4-(methythio)phenyl)phosphorothioate], diazinon [O,O-diethyl O-2-isopropyl-6-methylpyrimidin-4-yl phosphorothioate], chlorpyrifos [O,O-diethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate], acephate [O,S-dimethyl acetylphosphoramidothioate], methidathion [S-2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiadiazol-3-ylmethyl O,O-dimethylphosphorodithioate], disulfoton[O,O-diethylS-2-ethylthioethylphosphorothioate], DDVP [2,2-dichlorovinyl dimethyl phosphate], Sulprofos [O-ethyl O-4-(methylthio)phenyl S-propyl phosphorodithioate], cyanophos [O-4-cyanophenyl O,O-dimethyl phosphorothioate], dioxabenzofos [2-methoxy-4H-1,3,2-benzodioxaphosphinine-2-sulfide], dimethoate [O,O-dimethyl S-(N-methyl-carbamoylmethyl)dithiophosphate], phenthoate [ethyl 2-dimethoxyphosphinothioylthio(phenyl)acetate], malathion [diethyl (dimethoxyphosphinothioylthio))succinate], trichlorfon [dimethyl 2,2,2-trichloro-1-hydroxyethyl-phosphonate], azinphos-methyl [S-3,4-dihydro-4-oxo-1,2,3-benzotriazin-3-ylmethyl O,O-dimethyl phosphorodithioate], monocrotophos [dimethyl (E)-1-methyl-2-(methylcarbamoyl)-vinylphosphate], ethion [O,O,Oxe2x80x2,Oxe2x80x2-tetraethyl S,Sxe2x80x2-methylenebis(phosphorodithioate)], phosphothiazate [N-(O-methyl-S-sec-butyl)phosphorylthiazolidine-2-one] and the like; carbamate compounds such as BPMC (2-sec-butylphenyl methylcarbamate), benfracarb [ethyl N-[2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl (methyl)aminothio]-N-isopropyl-xcex2-alaninate], propoxur [2-isopropoxyphenyl N-methylcarbamate], Carbosulfan [2,3-dihydro-2,2-dimethyl-7-benzo[b]furanyl N-dibutylaminothio-N-methylcarbamate], carbaryl [1-naphthyl-N-methylcarbamate], methomyl [S-methyl-N-[(methylcarbamoyl)oxy]thioacetimidate], ethiofencarb [2-(ethylthiomethyl)phenylmethylcarbamate], aldicarb [2-methyl-2-(methylthio)propionaldehyde O-methylcarbamoyloxime], oxamyl [N,N-dimethyl-2-methyl-carbamoyloxyimino-2-(methylthio)acetamide], fenothiocarb [S-4-phenoxybutyl-N,N-dimethylthiocarbamate] and the like; pyrethroid compounds such as etofenprox [2-(4-ethoxyphenyl)-2-methylpropyl-3-phenoxybenzyl ether], fenvalerate [(RS)-xcex1-cyano-3-phenoxybenzyl (RS)-2-(4-chlorophenyl)-3-methyl-butyrate], esfenvalerate [(S)-xcex1-cyano-3-phenoxybenzyl (S)-2-(4-chlorophenyl)-3-methylbutyrate], fenpropathrin [(RS-xcex1-cyano-3-phenoxybenzyl 2,2,3, 3-tetramethylcyclopropanecarboxylate], cypermethrin [(RS)-xcex1-cyano-3-phenoxybenzyl (1RS)-cis,trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-carboxylate], permethrin [3-phenoxybenzyl (1RS)-cis, trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate], cyhalothrin [(RS)-xcex1-cyano-3-phenoxybenzyl (Z)-(1RS)-cis-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarboxylate], deltamethrin [(S)-xcex1-cyano-3-phenoxybenzyl (1R)-cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate], cycloprothrin [(RS)-xcex1-cyano-3-phenoxybenzyl (RS)-2,2-dichloro-1-(4-ethoxyphenyl)cyclopropanecarboxylate], fluvalinate [xcex1-cyano-3-phenoxybenzyl N-(2-chloro-xcex1, xcex1, xcex1-trifluoro-p-tolyl)-D-valinate], bifenthrin [2-methyl-biphenyl-3-ylmethyl (Z)-(1RS)-cis-3-(2-chloro-3,3,3-tri-fluoroprop-1-enyl)-2,2-dimethyl-cyclopropanecarboxylate], acrinathrin [cyano-(3-phenoxyphenyl)methyl [1R-{1xcex1(S*)-3xcex1(Z)}]-2,2-dimethyl-3-[3-oxo-3-(2,2,2-trifluoro-1-(tri-fluoromethyl)ethoxy-1-propenyl)cyclopropanecarboxylate], 2-methyl-2-(4-bromodifluoromethoxyphenyl)propyl 3-phenoxybenzyl ether, tralomethrin [(S)-xcex1-cyano-3-phenoxybenzyl (1R-cis)-3-{(1RS)(1,2,2,2-tetrabromoethyl)}-2,2-dimethyl-cyclopropanecarboxylate], silafluofen [(4-ethoxyphenyl)-{3-(4-fluoro-3-phenoxyphenyl)propyl} dimethylsilane] and the like; thiadiazine deribatives such as buprofezin [2-tert-butylimino-3-isopropyl-5-phenyl-1,3,5-triaziazinane-4-one]; nitroimidazolidine derivatives; nereistoxin derivatives such as cartap [S,Sxe2x80x2-(2-dimethylaminotrimethylene) bis(thiocarbamate)], thiocyclam [N,N-dimethyl-1,2,3-trithian-5-ylamine], bensultap [S,Sxe2x80x2-2-dimethylaminotrimethylene di (benzenethiosulfonate)] and the like;
N-cyanoamidine derivatives such as N-cyano-Nxe2x80x2-methyl-Nxe2x80x2-(6-chloro-3-pyridylmethyl)acetamidine and the like; chlorinated hydrocarbons such as endosulfan [6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepine oxide], xcex3-BHC [1,2,3,4,5,6-hexachlorocyclohexane], 1,1-bis(chlorophenyl)-2,2,2-trichloroethanol and the like; benzoylphenylurea compounds such as chlorfluazuron [1-(3,5-dichloro-4-(3-chloro-5-trifluoromethylpyridyn-2-yloxy)phenyl)-3-(2,6-difluorobenzoyl)urea], teflubenzuron [1-(3,5-dichloro-2,4-difluorophenyl)-3-(2,6-difluorobenzoyl)urea], flufenoxuron [1-(4-(2-chloro-4-trifluoromethylphenoxy)-2-fluorophenyl)-3-(2,6-difluorobenzoyl)urea and the like;
formamizine derivatives such as amitraz [N,Nxe2x80x2-[(methylimino)dimethylidine]-di-2,4-xylidine], chlordimeform [Nxe2x80x2-(4-chloro-2-methylphenyl)-N,N-dimethylmethinimidamide] and the like; thiourea derivatives such as diafenthiuron [N-(2,6-diisopropyl-4-phenoxyphenyl)-Nxe2x80x2-tert-butylcarbodiimide] and the like; phenylpyrazole derivatives; tebfenozide
[N-tert-butyl-Nxe2x80x2-(4-ethylbenzoyl)-3,5-dimethylbenzohydrazide], bromopropylate [isopropyl 4,4xe2x80x2-dibromobenzylate], tetradifon [4-chlorophenyl 2,4,5-trichlorophenylsulfone], quinomethionate [S,S-6-methylquinoxaline-2,3-diyldithiocarbonate], propargate [2-(4-tert-butylphenoxy)cyclohexylprop-2-yl sulfite], fenbutatin oxide [bis[tris(2-methyl-2-phenylpropyl)tin]oxide], hexythiazox [(4RS,5RS)-5-(4-chlorophenyl)-N-chlorohexyl-4-methyl-2-oxo-1,3-thiazolidin e-3-carboxamide], chlofentezine [3,6-bis(2-chlorophenyl)-1,2,4,5-tetrazine], pyridathioben [2-tert-butyl-5-(4-tert-butylbenzylthio)-4-chloropyridazine-3(2H)-one], fenpyroximate [Lert-butyl (E)-4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]-benzoate], tebfenpyrad [N-4-tert-butylbenzyl]-4-chloro-3-ethyl-1-methyl-5-pyrazolecarboxamide], polynactin complex [tetranactin, dinactin, trinactin], milbemectin, avermectin, ivermectin, azadilactin [AZAD], pyrimidifen [5-chloro-N-[2-{4-(2-ethoxyethyl)-2,3-dimethylphenoxy}ethyl]-6-ethylpyrimidine-4-amine], pymetrozine [2,3,4,5-tetrahydro-3-oxo-4-[(pyridin-3-yl)methyleneamino]-6-methyl-1,2,4-triazine] and the like.
The compound of the invention can control a variety of plant diseases, examples are described below: Blast (Pyricularia oryzae), Helminthosporium leaf spot (Cochliobolus miyabeanus) and sheath blight (Rhizoctonia solani) of rice plant; powderymildew (Erysiphegraminis), scab (Gibberella zeae), rust (Puccinia striiformis, P. graminis, P. recondita, P. hordei), snow blight (Typhula sp., Micronectriella nivalis), loose smut (Ustilago tritici, U. nuda), bunt (Tilletia caries), eyespot (Pseudocercosporella herpotrichoides), scald (Rhynchosporium secalis), leaf blight (Septoria tritici) and glume blotch (Leptosphaeria nodorum) of barley, wheat, oats and rye; melanose (Diaporthe citri), scab (Elsinoe fawcetti) and pencillium rot (Penicillium digitatum, P. italicum) of citrus; blossom blight (Sclerotinla mali), canker (Valsa mali), powdery mildew (Podosphaera leucotricha), Alternaria leaf spot (Alternaria mali) and scab (Venturia inaequalis) of apple; scab (Venturia nashicola, V. pirina), black spot (Alternaria kikuchiana) and rust (Gymnosporangium haraeanum) of pear; brown rot (Sclerotinia cinerea), scab (Cladosporium carpophilum) and Phomopsis rot (Phomopsis sp.) of peach; anthracnose (Elsinoe-ampelina), ripe rot (Glomerella cingulata), powdery mildew (Uncinula necator), rust (Phakopsora ampelopsidis), black rot (Guignardia bidwellii) and downy mildew (Plasmopara viticola) of grape; anthracnose (Gloeosporium kaki) and leaf spot (Cercospora kaki, Mycosphaerella nawae) of Japanese persimmon; anthracnose (Colletotrichum lagenarium), powdery mildew (Sphaerotheca fuliginea), gummy stem blight (Mycosphaerella melonis), stem rot (Fusarium oxysporum), downy mildew (Pseudoperonospora cubensis), late bright (Phytophthora sp.) and damping-off (Pythium sp.) of melons and cucumbers; early blight (Alternaria solani), leaf mold (Cladosporium fulvum) and late blight (Phytophthora infestans) of tomato; brown spot (Phomopsis vexans) and powdery mildew (Erysiphe cichoracearum) of eggplant; altenaria leaf spot (Alternaria japonica) and white spot (Cercosporella brassicae) of vegetables of Cruciferae; Welsh onion rust (Puccinia allii); purple stain (Cercospora kikuchii), Sphaceloma scab (Elsinoe glycines) and pod and stem blight (Diaporthe phaseolorum var. sojae) of soybean; kidney bean anthracnose (Colletotrichum lindemthianum); early leaf spot (Cercospora personata) and leaf spot (Cercospora arachidicola) of peanut; pea powdery mildew (Erysiphe pisi); early blight (Alternaria solani) and late blight (Phytophthora infestans) of potato; strawberry powdery mildew (Sphaerotheca humuli); net blister blight (Exobasidium reticulatum) and white scab (Elsinoe leucospila) of tea plant; brown spot (Alternaria longipes), powdery mildew (Erysiphe cichoracearum) anthracnose (Colletotrichum tabacum), downy mildew (Peronospora tabacina) and (Phytophthora nicotianae) of tobacco; beet leaf spot (Cercospora beticola); black spot (Diplocarpon rosae) and powdery mildew (Sphaerotheca pannosa) of rose; leaf spot (Septoria chrysanthemi-indici) and white rust (Puccinia horiana) of chrysanthemum; gray mold (Botrytis cinerea) and stem rot (Sclerotinia sclerotiorum) of various crops and the like.